CN104684671A - Surface-coated cutting instrument and method for producing same - Google Patents

Surface-coated cutting instrument and method for producing same Download PDF

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Publication number
CN104684671A
CN104684671A CN201380051121.2A CN201380051121A CN104684671A CN 104684671 A CN104684671 A CN 104684671A CN 201380051121 A CN201380051121 A CN 201380051121A CN 104684671 A CN104684671 A CN 104684671A
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Prior art keywords
layer
tib
coated cutting
area
base material
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CN201380051121.2A
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CN104684671B (en
Inventor
阿侬萨克·帕索斯
津田圭一
奥野晋
金冈秀明
市川乔启
森本浩之
伊藤实
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Sumitomo Electric Hardmetal Corp
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Sumitomo Electric Hardmetal Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C5/00—Milling-cutters
    • B23C5/16—Milling-cutters characterised by physical features other than shape
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/38—Borides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
    • B23B2228/10—Coatings
    • B23B2228/105—Coatings with specified thickness
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

Abstract

This surface-coated cutting instrument is one including a substrate and a coating formed on the substrate, wherein the coating contains one or more TiB2 layers, and the TiB2 layers contain TiB2 and Cl. This surface-coated cutting instrument is characterized in that the atomic ratio (Cl/(Ti+Cl)) of Ti and Cl in the TiB2 layers is higher in a first region than in a second region, given that the first region is a 0.5 mu m-thick region from the substrate-side interface, and the second region is a 0.5 mu m-thick region from the coating-surface-side interface.

Description

Surface-coated cutting tool and manufacture method thereof
Technical field
The present invention relates to the manufacture method of a kind of surface-coated cutting tool and this surface-coated cutting tool, wherein this surface-coated cutting tool comprises base material and is formed at the overlay film on this base material.
Background technology
Usually, known so a kind of surface-coated cutting tool, it comprises base material and is formed at the overlay film on this base material, in this surface-coated cutting tool, comprises TiB 2layer is as overlay film.
Such as, Japanese Patent Publication No.51-148713 (patent document 1) discloses a kind of wearability molded component, it superficial layer comprising hard alloy substrate and formed by the part layer of two-layer laminate, the part layer of this two-layer laminate comprises: the outside portion layering of being made up of aluminium oxide and/or zirconia; And inside portion layering (that is, the TiB to be made up of the diboride of the elements such as more than one boride, particularly titanium, zirconium and hafnium 2layer).
Inside portion layering in above-mentioned superficial layer is formed as the TiB of 3 μm 2layer, this TiB 2layer is by under the high temperature high vacuum condition of 1000 DEG C and 50 holders, introduces hydrogen, with 20mL/ hour introducing TiCl with 1900L/ hour 4and introduced BCl with 4g/ hour 3as reactive feedstock gas, and carry out film forming 1 hour thus obtain.In addition, the layering of described outside portion is formed as the alumina layer of 5 μm.
But, under the high temperature high vacuum condition in above-mentioned film forming procedure, bonding layer and TiB 2boron in layer can cause the formation of strong η layer and/or boracic brittle layer to the diffusion in hard alloy substrate, thus significantly shortens the life-span of this wearability molded component.
In order to solve the problem, propose a kind of so article coated, this is article coated by suppressing the diffusion of boron and making TiB 2tiB in layer 2micronize, thus improve wearability (Japanese patent publication No.2011-505261 (patent document 2)).Thisly article coatedly to be formed in the following way: wherein, the layer of 0.1 μm to 3 μm that makes by the group by titanium nitride, titanium carbonitride and boron titanium carbonitride covers the surface of cemented carbide base material, then forms the TiB of 1 μm to 5 μm 2layer.TiB in above-mentioned various layer 2the formation condition of layer is as follows.Specifically, utilization comprises the hydrogen of 10 volume %, the TiCl of 0.4 volume % 4, 0.7 volume % BCl 3with the feed gas component of the argon gas of 88.9 volume %, at the temperature of normal pressure and 800 DEG C, carry out thermal cvd 1 hour thus form the TiB that thickness is 2.5 μm 2layer.In this is article coated, do not form the boracic brittle layer caused to the diffusion in cemented carbide base material by boron, and TiB 2tiB in layer 2particle diameter be also controlled to below 50nm, therefore obtain prolongation to a certain extent life tools.
Reference listing
Patent document
Patent document 1: Japanese Patent Publication No.51-148713
Patent document 2: Japanese patent publication No.2011-505261
Summary of the invention
Technical problem
As mentioned above, the article coated life tools in patent document 2 obtain prolongation to a certain extent.But patent document 2 has only paid close attention to the suppression that formed strong η layer and/or boracic brittle layer or to TiB 2tiB in layer 2the control of particle diameter.Therefore, to TiB 2the further improvement of layer performance is limited, thus needs to consider from other angles.
In addition, when use this article coated the Ti system alloy as hard-cutting material is processed, especially tend in the processing raised in the temperature of cutting edge, and make the cutting edge of instrument tend to occur stress at the unique shape (zigzag) because of chip to concentrate and in the processing vibrated, the fracture of the hard coat caused because of various types of impact can cause bursting apart of tool cutting edges, thus significantly may shorten the life-span of instrument, thus need to improve further to cover film strength.
In view of above-mentioned condition completes the present invention.The object of this invention is to provide and comprise TiB 2layer is as the surface-coated cutting tool of overlay film, and the wearability of this surface-coated cutting tool and impact resistance obtain remarkable improvement.
The solution of problem
The present inventor conducts in-depth research to solve the problem, and found that, control TiB 2the concentration of chlorine contained in layer is very important for the raising of impact resistance.The present inventor studies further based on this discovery subsequently, thus completes the present invention.
Specifically, surface-coated cutting tool of the present invention comprises base material and is formed at the overlay film on described base material.Described overlay film at least comprises one deck TiB 2layer.This TiB 2layer comprises Cl and TiB 2.Assuming that at described TiB 2in layer, first area represents that thickness is the region of 0.5 μm from the interface of described substrate side, second area represents that thickness is the region of 0.5 μm from the interface of described overlay film face side, then the atomic ratio Cl/ (Ti+Cl) in described first area between Ti and Cl is greater than this atomic ratio in described second area.
In this case, the described atomic ratio Cl/ (Ti+Cl) in described first area is preferably 0.0001 to 0.01, and the described atomic ratio Cl/ (Ti+Cl) in described second area is preferably 0.00001 to 0.001.Described TiB 2the thickness of layer is preferably 1 μm to 10 μm.
In addition, the invention still further relates to a kind of method manufacturing surface-coated cutting tool, this surface-coated cutting tool comprises base material and is formed at the overlay film on this base material, and wherein said overlay film at least comprises one deck TiB 2layer.Described method comprises the described TiB of formation 2the step of layer.Described step at least comprises TiCl for being utilized by chemical vapour deposition technique 4and BCl 3unstrpped gas form described TiB 2the step of layer, and it is characterized in that: when described step starts, TiCl described in described unstrpped gas 4with described BCl 3between mol ratio TiCl 4/ BCl 3be equal to or greater than 0.6, and at the end of described step, this mol ratio TiCl 4/ BCl 3be less than 0.6.
Invention effect
Surface-coated cutting tool according to the present invention achieves the excellent effect significantly improving wearability and impact resistance.
Detailed description of the invention
To be described in more detail the present invention below.
< surface-coated cutting tool >
Surface-coated cutting tool of the present invention has such formation, and it comprises base material and is formed at the overlay film on base material.Preferably, this overlay film covers all surfaces of base material.But even if part thereof is not covered by this overlay film or the component part of this overlay film is different, this structure departs from the scope of the present invention not yet.
Above-mentioned surface-coated cutting tool of the present invention suitably can be used as cutting element, as drill bit, end mill(ing) cutter, drill bit cutting edge replaced type cutting tip, end mill(ing) cutter cutting edge replaced type cutting tip, milling cutting edge replaced type cutting tip, turning cutting edge replaced type cutting tip, metal saw, gear cutting tool, reamer and screw tap.
< base material >
As the base material for surface-coated cutting tool of the present invention, any material can be used, as long as this material is the base material as the above-mentioned type known traditionally.Such as, this base material is preferably any one in carbide alloy (such as, WC base cemented carbide or containing WC and Co or the material of carbonitride containing Ti, Ta, Nb etc.), cermet (primarily of formations such as TiC, TiN, TiCN), high-speed steel, pottery (titanium carbide, carborundum, silicon nitride, aluminium nitride, aluminium oxide etc.), cubic boron nitride sintered body, diamond sinter etc.
In the base material that these are various, particularly preferably be and select WC base cemented carbide and cermet (particularly TiCN based ceramic metal).This is because be excellent in the balance of these base materials between hardness and intensity (especially at high temperature), and there is the excellent specific property of the base material as the surface-coated cutting tool for such use.
When surface-coated cutting tool is cutting edge replaced type cutting tip etc., base material in this situation can be the base material having chip-breaking or do not have chip-breaking, and cutting edge ridgeline portions can be sharp edge (rib that rake face and rear knife face intersect each other), honing (being obtained to make it have curve (R) by processing sharp edge), negative land (negative land) ((beveling) obtains by splaying) and honing and negative land combination in any one shape.
< overlay film >
Overlay film of the present invention can comprise other layers, as long as it at least comprises one deck TiB 2layer.The example of other layers can comprise Al 2o 3layer, TiN layer, TiCN layer, TiBNO layer, TiCNO layer, TiAlN layer, TiAlCN layer, TiAlON layer, TiAlONC layer etc.In the present invention, will except TiB 2the composition of other layers beyond layer is expressed as in the situation of the chemical formula such as " TiN " and " TiCN ", and in the situation that the atomic ratio in chemical formula is not particularly limited, not think that the atomic ratio of each element is only " 1 ", but think and comprise the known atomic ratio of all routines.
This overlay film according to the present invention plays covering substrates to realize improving the effect of the effect of some characteristics such as wearability and impact resistance.
Desirably, the thickness of this overlay film of the present invention is 2 μm to 20 μm, is more preferably 5 μm to 15 μm.When thickness is less than 2 μm, wearability may be not enough.When thickness is more than 20 μm, when being subject to relatively strong stress in interrupted process between overlay film and base material, overlay film may peel off or impaired very continually.
<TiB 2layer >
TiB included in overlay film of the present invention 2the feature of layer is: TiB 2layer comprises Cl (chlorine) and TiB 2, and supposition is at TiB 2in layer, first area represents that thickness is the region of 0.5 μm from the interface of described substrate side, second area represents that thickness is the region of 0.5 μm from the interface of described overlay film face side, then the atomic ratio Cl/ (Ti+Cl) in described first area between Ti and Cl is greater than this atomic ratio in described second area.Owing to controlling the cl concn on thickness direction as mentioned above, therefore TiB of the present invention 2layer shows the excellent effect significantly improving wearability and impact resistance.This is because the amount of the Cl in second area be set as relatively little, higher hardness and intensity and better wearability can be obtained.On the other hand, the amount of the Cl in first area is set as relatively large, can hardness be reduced and improve traceability (followability).Namely, by inference, because the hardness in first area is lower, obtain buffering effect, even if therefore chap in the second area, be full of cracks also can alleviate in this first area, thus improves impact resistance, and improve combination of effects with the wearability of second area self, thus significantly improve wearability and impact resistance.
On the contrary, when running through whole TiB 2when Cl amount in layer is all less, hardness uprises, therefore excellent in abrasion resistance, and impact resistance reduces simultaneously.On the other hand, when running through whole TiB 2when Cl amount in layer is all larger, resistance to adherence and wearability all reduce.
By the reason that the thickness of first area and second area is all defined as 0.5 μm be: when this thickness is less than 0.5 μm, from the angle of analytical precision, sometimes fully cannot limit atomic ratio Cl/ (Ti+Cl).Therefore, from the angle of analytical precision, and the region of the characteristic of substrate side near interface can be reflected and second area representative can reflect the angle in the region of the characteristic of overlay film face side near interface the thickness in each region is defined as 0.5 μm from first area representative.When limiting atomic ratio Cl/ (Ti+Cl) in first area and second area, preferably, obtain the mean value of the numerical value (ratio) at the three or more individual different some place in each region, thus prevent measure error.
As mentioned above, TiB of the present invention 2layer is primarily of TiB 2(titanium diboride) is formed, and comprises Cl, and by control Cl energetically (conventional it is known that in the mill Cl as raw material residue and exist) concentration, have successfully been obtained above-mentioned excellent effect.To TiB 2in layer, the existing way of this Cl has no particular limits.Cl and TiB can be made 2be formed as solid solution, or can the form of free atom or ion exist.In addition, even if TiB of the present invention 2layer is containing removing TiB 2with the inevitable impurity outside Cl, this TiB 2layer also can not depart from scope of the present invention.
In this case, preferably, the atomic ratio Cl/ (Ti+Cl) in first area is 0.0001 to 0.01, and the atomic ratio Cl/ (Ti+Cl) in second area is 0.00001 to 0.001.It is further preferred that the atomic ratio Cl/ (Ti+Cl) in first area is 0.0001 to 0.005, and the atomic ratio Cl/ (Ti+Cl) in second area is 0.00001 to 0.0008.
Atomic ratio Cl/ (Ti+Cl) in first area is set to 0.0001 to 0.01, thus, the thermal shock and vibration that produce in overlay film forming process or in cutting process can be alleviated, thus improve impact resistance.
On the other hand, the atomic ratio Cl/ (Ti+Cl) in second area is set to 0.00001 to 0.001, which thereby enhances hardness, thus improve wearability.
In addition, desirably, TiB of the present invention 2the thickness of layer is 1 μm to 10 μm, and is more preferably 1.5 μm to 8 μm.When its thickness is less than 1 μm, TiB 2layer cannot play wearability fully in Continuous maching.When its thickness is more than 10 μm, impact resistance can not be made in interrupted cut to stablize.
Work as TiB 2when the thickness of layer is more than 1 μm, then between above-mentioned first area and second area, there is zone line.But, the composition (that is, atomic ratio Cl/ (Ti+Cl)) of this zone line is had no particular limits.This composition of zone line can be identical with the composition of above-mentioned first area, or can be identical with the composition of above-mentioned second area.Or this zone line can have the middle composition between above-mentioned first area and second area.In addition, the composition of this zone line can be greater than the atomic ratio Cl/ (Ti+Cl) of above-mentioned first area, or can be less than the atomic ratio Cl/ (Ti+Cl) of above-mentioned second area.This composition of zone line can change in a thickness direction.
At above-mentioned TiB of the present invention 2in layer, alleviate the impact occurred when cutting various workpiece (comprising the hard-cutting materials such as such as Ti alloy), and improve wearability.Therefore, wearability and impact resistance greatly improve, and hence improve the resistance to breaking property (breakage resistance) of instrument itself and extend its life-span.
< other layer of >
Overlay film of the present invention can comprise other layers and above-mentioned TiB 2layer.The example of these other layers can include but not limited to: the bottom be made up of TiN, TiC, TiBN etc., and it is directly formed at above base material to strengthen the joint between base material and overlay film further; TiCN layer, it is formed at described bottom and TiB 2to strengthen the joint between both between layer; Al 2o 3layer, it is formed at TiB 2to strengthen oxidative resistance on layer; The intermediate layer of being made up of TiCNO, TiBNO etc., it is formed at Al 2o 3layer and TiB 2to strengthen the joint between both between layer; The outermost layer be made up of TiN, TiCN, TiC etc., whether its outmost surface being formed at overlay film was used to indicate cutting edge.
Other layers above-mentioned can be formed as the thickness with 0.1 μm to 10 μm usually.
< manufacture method >
The invention still further relates to the method manufacturing surface-coated cutting tool, this surface-coated cutting tool comprises base material and is formed at the overlay film on this base material, and wherein this overlay film at least comprises one deck TiB 2layer.This manufacture method comprises formation TiB 2the step of layer.This step at least comprises TiCl for being utilized by chemical vapour deposition technique 4(titanium tetrachloride) and BCl 3the unstrpped gas of (boron chloride) forms TiB 2the step of layer, and it is characterized in that: when described step starts, TiCl in unstrpped gas 4with BCl 3between mol ratio TiCl 4/ BCl 3be equal to or greater than 0.6, and at the end of described step, this mol ratio TiCl 4/ BCl 3be less than 0.6.In other words, the TiB of the invention described above 2layer is formed by this manufacture method.
Like this, manufacturing method according to the invention, at formation TiB 2in the step of layer, when step starts and at the end of step, TiCl in unstrpped gas 4with BCl 3between mol ratio TiCl 4/ BCl 3difference, can form the TiB with above-mentioned feature thus 2the structure of layer.About TiB 2layer constructs the reason with above-mentioned feature structure by adopting above-mentioned condition, it be unclear that detailed mechanism.But, it is believed that this is because work as TiB 2layer crystal growth time, TiCl in unstrpped gas 4and BCl 3the splitting status of middle Cl, volatileness and disengaged position are with TiCl 4with BCl 3between mol ratio difference and change, therefore TiB 2in layer, the content ratio of Cl changes.
In this regard, as long as mol ratio TiCl when step starts 4/ BCl 3be equal to or greater than 0.6, and mol ratio TiCl at the end of step 4/ BCl 3be less than 0.6, then can obtain the TiB with the present invention's structure 2layer.But this mol ratio can change from the beginning to the end gradually, or change in any time point in this step.
In addition, preferably, mol ratio TiCl 4/ BCl 3demonstrate greatest measure when step starts, and at the end of demonstrate minimum value.But, mol ratio TiCl 4/ BCl 3minimum of a value and maximum can be demonstrated by any time point in step.
In addition, as TiB of the present invention 2when layer has zone line between above-mentioned first area and second area, the composition (that is, atomic ratio Cl/ (Ti+Cl)) of this zone line is with mol ratio TiCl in unstrpped gas 4/ BCl 3above-mentioned change and tend to change.
Above-mentioned manufacture method is set forth in more detail, TiB 2in layer forming step, raw materials used gas (also referred to as reacting gas) can be TiCl 4, BCl 3, H 2and Ar.TiCl when step starts 4and BCl 3mol ratio TiCl 4/ BCl 3need to be equal to or greater than 0.6, be preferably equal to or greater than 1.0 in addition.This is because when mol ratio is less than 0.6, the atomic ratio Cl/ (Ti+Cl) in first area diminishes, thus is difficult to make atomic ratio in first area higher than the atomic ratio in second area.Preferably, mol ratio TiCl when step starts 4/ BCl 3be equal to or less than 10.This is because, as mol ratio TiCl 4/ BCl 3during more than 10, the atomic ratio Cl/ (Ti+Cl) in first area more than 0.01, and demonstrates the tendency that cannot obtain desirable strength.In addition, reaction efficiency significantly reduces and deposits a large amount of unreacting substance, and operation self cannot continue.
On the other hand, the mol ratio TiCl at the end of step 4/ BCl 3need to be less than 0.6, in addition, it is preferably less than 0.5.This is because when mol ratio is equal to or greater than 0.6, the atomic ratio Cl/ (Ti+Cl) in second area is greater than 0.001, then resistance to impact becomes not enough.Preferably, mol ratio TiCl at the end of step 4/ BCl 3be equal to or greater than 0.1.This is because when mol ratio is less than 0.1, TiB 2sedimentation rate significantly reduce, thus be difficult to produce needed for TiB 2film.
As mentioned above, by TiB 2the mol ratio TiCl of unstrpped gas at the end of layer forming step 4/ BCl 3be set smaller than mol ratio during beginning, thus the TiB with said structure can be formed 2layer.
Preferably, by the H in above-mentioned raw materials gas 2be set as about 70 % by mole to 99 % by mole, Ar be set as about 0 % by mole to 20 % by mole (that is, can not Ar be comprised in some cases).As mentioned above, with volume basis, H 2the major part in unstrpped gas is occupied with Ar.
In addition, the reaction temperature in this step is set to 800 DEG C to 950 DEG C, is more preferably 850 DEG C to 900 DEG C.When reaction temperature is less than 800 DEG C, be difficult to be formed the TiB with feature of the present invention 2layer.When reaction temperature is more than 950 DEG C, TiB 2can coarse be there is, if or base material be made up of carbide alloy, then may generate strong η layer (WCoB layer) and boracic brittle layer (CoB layer).In this regard, manufacture method of the present invention has the excellent effect that can prevent from generating strong η layer and boracic brittle layer.
For TiB according to the present invention 2layer, as long as have employed above-mentioned condition, other conditions (as pressure) can adopt known condition and without particular limitation.In addition, when overlay film of the present invention comprises except TiB 2layer beyond other layer time, form these layers by known chemical vapour deposition technique and physical vaporous deposition.Although have no particular limits its formation method, from can a chemical vapor deposition unit with TiB 2layer forms the angle of these layers together continuously, forms these layers preferably by chemical vapour deposition technique.
Embodiment
Although hereinafter with reference to embodiment, the present invention will be described in more detail, and the present invention is not limited thereto.
The preparation > of < base material
Base material A and B of preparation shown in following table 1.Specifically, the material powder Homogeneous phase mixing mixing composition shown in table 1 will be had, after carrying out being compressed and molded into predetermined shape, at 1300 DEG C to 1500 DEG C, sinter 1 to 2 hour, thus obtain the hard alloy base material being formed as comprising these two kinds of shapes of CNMG120408NUX and SEET13T3AGSN-G.In other words, two kinds of different shapes all prepared by often kind of base material.
Above-mentioned two kinds of shapes manufacture by Sumitomo Electric Hardmetal company.CNMG120408NUX is the shape of turning cutting edge replaced type cutting tip, and SEET13T3AGSN-G is the shape of rotary cut (milling) cutting edge replaced type cutting tip.
[table 1]
The formation > of < overlay film
The substrate surface of above-mentioned preparation forms overlay film.Specifically, base material is placed in chemical vapor deposition unit, thus on base material, forms overlay film by chemical vapour deposition technique.The formation condition of overlay film, as described in following table 2 and 3, regulates film formation time to obtain each thickness described in table 4.Table 2 shows except TiB 2the formation condition of other each layers outside layer, table 3 shows TiB 2the formation condition of layer.In addition, TiBNO and TiCNO in table 2 is the intermediate layer in aftermentioned table 4, and other compounds also correspond respectively in table 4 except TiB 2other layers (formation condition of TiCN layer is identical with the formation condition as outermost TiCN layer) outside layer.
In addition as shown in table 3, for TiB 2layer has 7 kinds of formation conditions " a " to " e " and " x " to " y ", and its conditional " a " to " e " is for meeting the condition of the inventive method, and condition " x " to " y " is for meeting the condition of comparative example (routine techniques).In addition, the unstrpped gas composition that " during beginning " is described in hurdle is used for TiB 2the first half of whole film formation times that layer is formed, " at the end of " described unstrpped gas composition is used for latter half in a hurdle.
Such as, formation condition " a " shows the TiCl employing in composition in first half and comprise 2.5 % by mole 4, the BCl of 3.7 % by mole 3with the H of 93.8 % by mole 2unstrpped gas (reacting gas), and in latter half, employ in composition the TiCl comprising 2.0 % by mole 4, the BCl of 3.7 % by mole 3with the H of 94.3 % by mole 2unstrpped gas (reacting gas), thus be 80.0kPa and temperature forms TiB by chemical vapour deposition technique under being the condition of 850 DEG C at pressure 2layer.Mol ratio TiCl in each unstrpped gas composition 4/ BCl 3as shown in table 3.TiB 2the composition recorded in layer forming step consisting of when starting " during beginning " in table 3 one hurdle, and at the end of to consist of in table 3 " at the end of " composition recorded in a hurdle.
In addition, the TiB shown in table 2 is formed in a similar manner 2other each layers beyond layer, difference is the composition of non-feed change gas in film forming procedure.It should be noted that " surplus " in table 2 represents H 2occupy the remainder of unstrpped gas (reacting gas).In addition, " gas gross " represents that, when this gas is perfect gas under supposition standard state (0 DEG C, 1 atmospheric pressure), in the unit interval, gas introduces the total volume flow rate of the gas in CVD stove.
In addition, the composition detecting each overlay film by SEM-EDX (ESEM-energy dispersion type X-ray spectrum) (comprises TiB 2atomic ratio Cl/ (Cl+Ti) in layer).As each atomic ratio Cl/ (Cl+Ti) in first area and second area, each use the atomic ratio by measuring three some places in each region and the mean value of value that obtains.Its result is as shown in table 3.
<TiB 2the stripping time of origin > of layer
Measure TiB in the following manner 2the stripping time of origin of layer.
First, use the CNMA12008 of rounding (being manufactured by Sumitomo Electric Hardmetal Co., Ltd.) as base material, and its surface (Ra≤0.5 μm) of polishing, subsequently in table 3 under described condition, base material directly forms the TiB that thickness is 5 μm 2layer.Then, under the compressed air of 0.3MPa, be that 20% aqueous dispersions of the spherical alumina of 100 μm is injected into aforementioned TiB by comprising average grain diameter 2layer (distance between base material (cutting edge crest line) and spout is set as 30mm), and utilize microscopic examination TiB 2the breaking state of layer (cutting edge ridgeline portions).
Then measure until TiB 2time (second) when layer is peeled off or ruptures.Time is longer, TiB 2layer is more excellent to the zygosity of base material, and impact resistance is better.The results are shown in table 3.
The manufacture > of < surface-coated cutting tool
On base material, overlay film is formed above, thus obtained embodiment 1 to 20 below shown in table 4 and the surface-coated cutting tool (often kind of overlay film forms two kinds of cutting edge replaced type cutting tips (substrate shapes is different)) in comparative example 1 to 7 by the condition in the table 2 and 3 that illustrates.
Such as, illustrate in table that the surface-coated cutting tool of embodiment 4 has such formation, wherein have employed the base material A shown in table 1 as base material, and to define thickness under condition shown in table 2 on the surface of base material A be that the TiN layer of 0.5 μm is as bottom, on the surface of TiN layer, define the TiCN layer that thickness is 2.0 μm under condition shown in table 2, under the formation condition " c " in table 3, in TiCN layer, form the TiB that thickness is 2.5 μm 2layer, at TiB under condition shown in table 2 2layer to be formed successively thickness be the TiBNO layer of 0.5 μm is the Al of 1.5 μm as intermediate layer, thickness 2o 3layer and thickness be the TiN layer of 0.8 μm as outermost layer, on base material, define the overlay film that gross thickness is 7.8 μm thus.
In addition, due to all TiB of comparative example 1 to 7 2layer is all formed under the condition not based on the routine techniques of the inventive method, therefore these TiB 2layer and the not shown formation similar with the present invention (that is, atomic ratio Cl/ (Ti+Cl) does not change, and is certain in a thickness direction.See table 3).
The blank column that it should be noted that in table 4 represents and does not form relevant layers.
[table 4]
< cutting test >
The surface-coated cutting tool of above-mentioned acquisition is used for carry out following four kinds of cutting tests.
< cutting test 1>
For each surface-coated cutting tool (employing those surface-coated cutting tools that shape is CNMG120408NUX) of the embodiment shown in following table 5 and comparative example, to measure under following machining condition until cutting time when tool flank wear (Vb) reaches 0.25mm, and observe the final faulted condition of cutting edge.The results are shown in table 5.The results show the cutting time longer, wearability is more excellent.In addition, this result also shows, final faulted condition is more close to normal wear state, then impact resistance is more excellent.
< machining condition >
Workpiece: Ti6Al4V pole periphery is cut
Peripheral speed: 70m/ minute
Feed speed: 0.15mm/rev
Cutting output: 1.5mm
Cutting fluid: exist
[table 5]
As can be seen from Table 5, the wearability of the surface-coated cutting tool of the embodiment of the present invention and impact resistance are obviously better than the surface-coated cutting tool of comparative example.
In addition, in final faulted condition in table 5, " normal wear " represent only by wear and tear the faulted condition that causes and do not burst apart, fracture etc. (there is smooth wear surface), and " bursting apart " represents in cutting edge part, there occurs minimum part of bursting apart.
< cutting test 2>
For each surface-coated cutting tool (employing the surface-coated cutting tool that shape is CNMG120408NUX) of the embodiment shown in following table 6 and comparative example, to measure under following machining condition until cutting time when tool flank wear (Vb) reaches 0.25mm, and observe the final faulted condition of cutting edge.The results are shown in table 6.The results show the cutting time longer, wearability is more excellent.This result also shows, final faulted condition is more close to normal wear state, then impact resistance is more excellent.
< machining condition >
Workpiece: INCONEL 718 pole periphery is cut
Peripheral speed: 50m/ minute
Feed speed: 0.15mm/rev
Cutting output: 1.5mm
Cutting fluid: exist
[table 6]
As can be seen from Table 6, the wearability of the surface-coated cutting tool of the embodiment of the present invention and impact resistance are obviously better than the surface-coated cutting tool of comparative example.
In final faulted condition in table 6, " normal wear " represent only by wear and tear the faulted condition that causes and do not burst apart, fracture etc. (there is smooth wear surface), and " leading edge slightly ruptures " expression creates minimum part of bursting apart in the cutting edge part forming final face, and wherein identifiable design goes out exposed base material in the portion.
< cutting test 3>
For each surface-coated cutting tool (employing the surface-coated cutting tool that shape is SEET13T3AGSN-G) of the embodiment shown in following table 7 and comparative example, to measure under following machining condition until occur fracture or until when tool flank wear (Vb) reaches 0.25mm by frequency (pass frequency) and cutting distance, and observe the final faulted condition of cutting edge.The results are shown in table 7.
In addition, it is the number of repetition of the operation repeated by frequency, wherein carry out by one end of this side to the rotary-cut (it should be noted that being met by frequency representation above-mentioned condition in by one end to the process of the other end with decimal point in numerical value) of the other end with the side (surface of 300mm × 80mm) of cutter to following workpiece (bulk of shape: 300mm × 100mm × 80mm) being connected with a surface-coated cutting tool (cutting edge replaced type cutting tip).In addition, cut apart from representing until total distance that when above-mentioned condition is met, workpiece is cut, it is equivalent to the product by frequency and above-mentioned side length (300mm).
This result shows, by frequency larger (that is, cutting distance longer), wearability is more excellent.In addition, this result also show final faulted condition more close to normal wear state, then impact resistance is more excellent.
< machining condition >
Workpiece: Ti6Al4V bulk material
Peripheral speed: 80m/ minute
Feed speed: 0.25mm/s
Cutting output: 1.0mm
Cutting fluid: exist
Cutter: WGC4160R (being manufactured by Sumitomo Electric Hardmetal Co., Ltd.)
Blade linking number: 1
[table 7]
Pass through frequency Cut distance (m) Final faulted condition
Embodiment 5 23.0 6.9 Normal wear
Embodiment 12 19.5 5.9 Normal wear
Embodiment 14 25.0 7.5 Normal wear
Embodiment 15 21.0 6.3 Normal wear
Embodiment 20 20.0 6.0 Normal wear
Comparative example 4 15.0 4.5 Normal wear
Comparative example 6 6.0 1.8 Fracture
As can be seen from Table 7, the wearability of the surface-coated cutting tool of the embodiment of the present invention and impact resistance are obviously better than the surface-coated cutting tool of comparative example.
In addition, in final faulted condition in table 7, " normal wear " represent only by wear and tear the faulted condition that causes and do not burst apart, fracture etc. (there is smooth wear surface); " fracture " represents the larger part of bursting apart produced in cutting edge part.
< cutting test 4>
For each surface-coated cutting tool (employing those surface-coated cutting tools that shape is SEET13T3AGSN-G) of the embodiment shown in following table 8 and comparative example, to measure under following machining condition until occur fracture or until when tool flank wear (Vb) reaches 0.25mm by frequency and cut distance, and observe the final faulted condition of cutting edge.The results are shown in table 8.
In addition, the same with cutting test 3, it is the number of repetition of the operation repeated by frequency, wherein carry out by one end of this side to the rotary-cut (it should be noted that being met by frequency representation above-mentioned condition in by one end to the process of the other end with decimal point in numerical value) of the other end with the side (surface of 300mm × 80mm) of cutter to following workpiece (bulk of shape: 300mm × 100mm × 80mm) being connected with a surface-coated cutting tool (cutting edge replaced type cutting tip).The same with cutting test 3, cut apart from also representing until total distance that when above-mentioned condition is met, workpiece is cut, it is equivalent to the product by frequency and above-mentioned side length (300mm).
This result shows, by frequency larger (that is, cutting distance longer), then wearability is more excellent.In addition, this result also shows, final faulted condition is more close to normal wear state, then impact resistance is more excellent.
< machining condition >
Workpiece: SUS304 bulk material
Peripheral speed: 150m/ minute
Feed speed: 0.2mm/s
Cutting output: 1.0mm
Cutting fluid: exist
Cutter: WGC4160R (being manufactured by Sumitomo Electric Hardmetal Co., Ltd.)
Blade linking number: 1
[table 8]
Pass through frequency Cut distance (m) Final faulted condition
Embodiment 8 21.7 6.5 Normal wear
Embodiment 9 19.5 5.9 Normal wear
Embodiment 11 18.0 5.4 Normal wear
Embodiment 18 20.0 6.0 Normal wear
Embodiment 19 17.8 5.3 Normal wear
Comparative example 5 15.0 4.5 Normal wear
Comparative example 7 7.0 2.1 Fracture
As can be seen from Table 8, the wearability of the surface-coated cutting tool of the embodiment of the present invention and impact resistance are obviously better than the surface-coated cutting tool of comparative example.
In addition, in final faulted condition in table 8, " normal wear " represent only by wear and tear the faulted condition that causes and do not burst apart, fracture etc. (there is smooth wear surface); " fracture " represents the larger part of bursting apart produced in cutting edge part.
Although be illustrated embodiment of the present invention and embodiment as mentioned above, from be just intended to the formation of above-mentioned embodiment and embodiment to combine rightly.
Should be understood that, embodiment disclosed herein and embodiment are exemplary and nonrestrictive in each.Scope of the present invention is limited by the claim of claims instead of explanation above, and is intended to comprise any amendment in the scope and implication that are equal to the claim of claims.

Claims (4)

1. a surface-coated cutting tool, comprising:
Base material; And
Be formed at the overlay film on described base material,
Described overlay film at least comprises one deck TiB 2layer,
Described TiB 2layer comprises Cl and TiB 2, and
Assuming that at described TiB 2in layer, first area represents that thickness is the region of 0.5 μm from the interface of described substrate side, second area represents that thickness is the region of 0.5 μm from the interface of described overlay film face side, then the atomic ratio Cl/ (Ti+Cl) in described first area between Ti and Cl is greater than this atomic ratio in described second area.
2. surface-coated cutting tool according to claim 1, wherein
Described atomic ratio Cl/ (Ti+Cl) in described first area is 0.0001 to 0.01, and the described atomic ratio Cl/ (Ti+Cl) in described second area is 0.00001 to 0.001.
3. surface-coated cutting tool according to claim 1 and 2, wherein
Described TiB 2the thickness of layer is 1 μm to 10 μm.
4. manufacture a method for surface-coated cutting tool, this surface-coated cutting tool comprises base material and is formed at the overlay film on this base material, and described overlay film at least comprises one deck TiB 2layer, described method comprises:
Form described TiB 2the step of layer,
Described step at least comprises TiCl for being utilized by chemical vapour deposition technique 4and BCl 3unstrpped gas form described TiB 2the step of layer, and
When described step starts, TiCl described in described unstrpped gas 4with described BCl 3between mol ratio TiCl 4/ BCl 3be equal to or greater than 0.6, and at the end of described step, this mol ratio TiCl 4/ BCl 3be less than 0.6.
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